Laminated light-blocking decorative articles

ABSTRACT

Laminated light-blocking decorative articles are prepared by applying an aqueous foamed opacifying composition to a non-woven fabric, drying, laminating a decorative fabric to the resulting dry foamed opacifying layer, and densifying that layer to have a thickness that is at least 20% less than before densifying. This operation can be carried out so that non-woven fabric, decorative fabric, and aqueous foamed opacifying composition are supplied in a single-pass, in-line operation to make any desired quantity of a laminated light-blocking decorative article. The applied aqueous foamed opacifying composition has 35%-70% solids and a foam density of 0.1-0.5 g/cm3. It is composed of (a) porous particles, (b) a binder material, (c) two or more additives comprising at least one foaming surfactant and at least one foam stabilizer, (d) an aqueous medium, and (e) at least 0.0001 weight % of an opacifying colorant that absorbs electromagnetic radiation having a wavelength of 380-800 nm.

RELATED APPLICATIONS

This is a divisional of application Ser. No. 16/720,041, filed Dec. 19,2019, now U.S. Pat. No. ______.

Reference is made to the following related applications:

U.S. Pat. No. 10,942,300 issued Mar. 9, 2021, to Nair and Brick;

U.S. Pat. No. 11,275,203 issued Mar. 15, 2022, to Nair and Brick;

U.S. Publication No. 2021/0189640, dated Jun. 24, 2021, by Nair andHerrick; and

U.S. Pat. No. 11,181,247 issued Nov. 23, 2021 to Nair, the disclosuresof all of which are incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to the field of light-blocking materials. Inparticular, this invention relates to a method for making laminatedlight-blocking decorative articles having opacifying or light-blockingproperties, which articles can be used as decorative drapes, shades,blinds, or other light-blocking materials. Such laminated light-blockingdecorative articles can be prepared using a single-pass, in-linemanufacturing operation by coating a non-woven fabric with an aqueousfoamed opacifying composition, followed by drying, lamination to adecorative fabric, and densifying the resulting dry foamed opacifyinglayer. This invention also relates to laminated light-blockingdecorative articles prepared using the noted method.

BACKGROUND OF THE INVENTION

In general, when light strikes a surface, some of it may be reflected,some absorbed, some scattered, and the rest transmitted. Reflection canbe diffuse such as light reflecting off a rough surface like a whitewall, in all directions, or specular, as in light reflecting off amirror at a definite angle. A 100% opaque substance transmits almost nolight, and therefore reflects, scatters, or absorbs all of it. Bothmirrors and carbon black are opaque. Opacity depends on the selectiveabsorption of the frequency of the light being considered. “Blackout” orlight blocking materials typically refer to coated layers in articlesthat are substantially impermeable to light such as visible and UVradiation. Thus, when a blackout material such as a blackout curtain orblackout shade is hung over a window, it generally blocks substantiallyall external light from entering the room through that window. Blackoutmaterials are suitable as curtains or shades for use in homes, forinstitutional use in hospitals and nursing homes and offices, as well asfor use in commercial establishments such as hotels, theaters, andaircraft windows where the option of excluding light can be desirable.

Light blocking articles such as the blackout curtains can be comprisedof a fabric (porous substrate) coated with several layers of alight-blocking composition. There is a need for these curtains, inaddition to blocking transmitted light, to have a light color (hue)facing the environment to aid in illumination to minimize the amount ofartificial lighting needed to perform the activity. An example is whenthe function of the blackout material is to separate two areas ofactivity where one or both areas can be artificially lit at the sametime. More often than not, the function of a blackout curtain is toprevent sunlight from entering a room through a window. It can also bedesirable for the color (hue) of the side facing the window to match theexterior décor of the building.

Light colored blackout coatings theoretically can be made by coatingporous fabrics with light colored foams containing light scatteringpigments such as titanium dioxide or clays. However, using only thesepigments, very thick foam coatings will be needed to create blackoutcurtains through which the sun is not visible in a darkened room using.One method that is practiced for reducing the weight of such blackoutmaterials is to sandwich a light-absorbing, foamed black or greypigment, such as a carbon black between two foamed light scattering,white pigment-containing layers.

When an electromagnetic radiation blocking coating has, as it oftendoes, a strongly light absorbing material containing black pigments suchas carbon black, between two reflective layers, it has at least twodistinct problems. First, such materials require three or more separatecoating operations that reduce manufacturing productivity and increaseunit costs. Secondly, carbon black in the light absorbing middle layercan become “fugitive” during sewing or handling as a result of somepuncture or tear, and soil other layers such as the reflective layers,which is highly objectionable. Additionally, the stitches generated inthe materials during sewing can cause the fugitive carbon black from thelight absorbing layer to spread over a larger area thereby increasingthe area of objectionable contamination of the light-colored surface.

U.S. Pat. No. 9,891,350 (Lofftus et al.) describes improved articlesthat are designed with an opacifying layer applied to a substrate andthat are capable of blocking predetermined electromagnetic radiation.

An improvement in this art is described in U.S. Pat. No. 9,469,738 (Nairet al.) in which small amounts of porous particles containing smallamounts of opacifying colorants can be incorporated into foamedcompositions that have a foam density of at least 0.1 g/cm³. Such foamedcompositions can be applied to a substrate to provide opacification.U.S. Pat. No. 9,963,569 (Nair et al) describes similar technology formaking opacifying element using a foamed aqueous latex composition.

U.S. Pat. No. 6,884,491 (Rubin et al.) describes water repellant, waterresistant, and stain resistant fabrics that are prepared using treatingcompositions that are laminated to a backing polymeric film.

It is known to make decorative articles such as draperies using backingliners formed from woven or non-woven fabrics. A typical drapery can bea rectangular piece of decorative fabric whose edges are folded back andhemmed. A drapery made from a single layer of decorative textile fabricis less expensive than a lined drapery but it suffers from thedifficulty that it is not fully opaque and that sunlight transmissioncan cause fading of dyes in the drapery as well in other articles orprevent desired darkening in a room which the drapery is hung. A lineddrapery is generally constructed from a relatively high qualitydecorative fabric that can be printed, embossed, or otherwise carries adesign, together with a lining that can be formed from a suitable lessexpensive woven or non-woven fabric. Such lining functions to reduce thetransmission of light to impact the expensive decorative fabric. Thelining can also add opacity to make it more difficult for outsiders tosee into a room, and it may also provide insulative properties bytrapping air between it and the decorative fabric. In addition, a liningcan also add some weight to a drapery so that it hangs better. However,lined draperies are more expensive not just because of additionalmaterial but because of fabrication costs to attach the lining to thedecorative fabric.

A number of solutions have been proposed in the industry to reduce thecosts and to achieve the advantages of linings, including the use offoamed linings or foamed adhesives between decorative fabrics andlinings. A composite lining comprises a typical inexpensive woven ornon-woven material useful as a backing material and a foamed organicpolymer that functions as an adhesive for a decorative textile fabric,as described for example, in U.S. Pat. No. 3,748,217 (May et al.). Thefoamed organic polymer can be applied to a decorative fabric before theinexpensive woven or non-woven or material is laminated to thedecorative textile fabric-adhesive combination, followed by curing.

Decorative blackout draperies are described in U.S. Pat. No. 5,741,582(Lederman et al.) in which an opaque adhesive is applied to a textilematerial (first substrate) and a second material (second substrate) isthen adhered thereto to provide a decorative drapery surface on one sideand a lining on the opposing side of the opaque adhesive. The opposingmaterials can be formed from any suitable woven or non-woven textilecomposed of naturally-occurring or man-made fibers. The opaque adhesivecan be provided as an acrylic foam containing a black or dark pigment,which acrylic foam is eventually crushed and cured once coated. Multipleadhesive layers can be used if desired, as applied to opposing first andsecond substrates. Unfortunately, the black or dark pigment in theopaque adhesive layer can show through both textiles that sandwich itand add discoloration to the fabric, unless outer layers of white foamare coated on either side of the black foam to hide that layer andminimize both coloration and fugitive black pigments such as carbonblack. This becomes a multistep expensive process that could compromisethe decorative fabric during the coating processes.

Decorative fabrics can also be prepared by providing opacifyingcompositions on their backside and then applying a flock to theopacifying composition for feel and appearance. However, manymanufacturers and convertors are not happy with the use of flock becauseit can dust off the article during various down-stream treatments andbecome a product contaminant and an environmental health hazard for itsflammability and human inhalation of particulate fibers. Moreover, it ishard to apply flock in a uniform manner unless it is applied usingelectrostatic means and apparatus, which is a very expensive operation.Thus, there is a need to avoid the use of flock if possible.

There is also a need for an improved and inexpensive means to providelight-blocking decorative articles in which flock is avoided but desiredfabric feel is achieved on both faces of the article in a simplified,single-pass in-line process. There is also a need to avoid subjectingdecorative fabrics to handling stresses during coating and dryingprocesses while trying to achieve a light blocking article with thedesired look and feel.

SUMMARY OF THE INVENTION

The present invention provides a laminated light-blocking decorativearticle comprising:

a decorative fabric having a face side and a back side, a dry foamedlayer, and a non-woven fabric having a face side and a back side,wherein the decorative fabric is laminated on its back side to the dryfoamed opacifying layer that is disposed on the back side of thenon-woven fabric,

the dry foamed opacifying layer present at a dry coverage of less thanor equal to 1000 g/m², and comprising:

(a) porous particles in an amount of at least 0.1 weight % and up to andincluding 35 weight %, each porous particle comprising a continuouspolymeric phase and discrete pores dispersed within the continuouspolymeric phase, the porous particles having a mode particle size of atleast 2 μm and up to and including 50 μm and a porosity of at least 20volume % and up to and including 70 volume %;

(b) a matrix material that is derived from a (b) binder material, whichmatrix material is present in an amount of at least 10 weight % and upto and including 80 weight %,

(c) two or more additives in an amount of at least 0.0001 weight % andup to and including 50 weight %, the two or more additives comprising atleast one foaming surfactant and at least one foam stabilizer,

(d) an aqueous medium in an amount of less than 5 weight %, and

(e) an opacifying colorant in an amount of at least 0.002 weight % andup to and including 2 weight %, which opacifying colorant being adifferent material from the (a) porous particles, (b) binder material,and (c) two or more additives, and which opacifying colorant absorbselectromagnetic radiation having a wavelength of at least 380 nm and upto and including 800 nm,

all amounts of (a) porous particles, (b) binder material, (c) two ormore additives, and (e) opacifying colorant being based on the totalweight of the dry foamed opacifying composition.

The present invention provides a laminated light-blocking decorativearticle that can be prepared in-line in a single-pass operation bybringing together a coated non-woven fabric and a decorative fabric inlamination. Before lamination, the back side of the non-woven fabric iscoated with a single aqueous foamed opacifying composition havingdesired opacity and optionally adhesive properties, to provide a singledry foamed opacifying layer that can be adhered in-line to thedecorative fabric to provide a laminated light blocking decorativearticle with the desired black-out, look, and feel properties. Thepresent invention can be prepared using a simplified workflow where thedecorative fabric is not subjected to coating and drying stresses andwhere the single-pass, in-line lamination avoids the extra steps ofcrushing and curing the coated non-woven fabric and storing of excessinventory. The process can also avoid the need for a laminating adhesiveby effecting crushing, curing, and lamination in a single step.

The non-woven fabrics used in this invention can be customized to havevarious features including printed images and colors.

Moreover, while flock and its problems are avoided, the resultinginventive laminated light-blocking decorative articles are soft to thetouch, and can be designed with any desired weight, stiffness (forexample, for used as roller shades), or coloration while sufficientlyblocking out impinging light. Decorative fabrics used in themanufacturing operation are spared from the risk and expense ofstressful coating operations and multiple passes with stretching ortentering.

DETAILED DESCRIPTION OF THE INVENTION

The following discussion is directed to various embodiments of thepresent invention and while some embodiments can be desirable forspecific uses, the disclosed embodiments should not be interpreted orotherwise considered to limit the scope of the present invention, asclaimed below. In addition, one skilled in the art will understand thatthe following disclosure can have broader use than is explicitlydescribed or discussed for any particular embodiment.

Definitions

As used herein to define various components of the aqueous foamedopacifying composition or dry foamed opacifying layer, that is the (a)porous particles, (b) binder materials, (c) two or more additives, (e)opacifying colorant, and other materials used in the practice of thisinvention, and unless otherwise indicated, the singular forms “a,” “an,”and “the” are intended to include one or more of the components (thatis, including plurality referents).

Each term that is not explicitly defined in the present application isto be understood to have a meaning that is commonly accepted by thoseskilled in the art. If the construction of a term would render itmeaningless or essentially meaningless in its context, the term shouldbe interpreted as having a standard dictionary meaning.

The use of numerical values in the various ranges specified herein,unless otherwise expressly indicated otherwise, are to be considered asapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this manner,slight variations above and below the stated ranges may be useful toachieve substantially the same results as the values within the ranges.In addition, the disclosure of these ranges is intended as a continuousrange including every value between the minimum and maximum values aswell as the end points of the ranges.

Unless otherwise indicated, the terms “dry foamed opacifyingcomposition” and “dry foamed opacifying layer” are intended to refer tothe same feature.

The terms “porous particle” and “porous particles” are used herein,unless otherwise indicated, to refer to porous bead-like polymericmaterials useful in the aqueous foamed opacifying compositions essentialfor the present invention. As defined in detail below, the porousparticles generally comprise a solid continuous polymeric phase havingan external particle surface and discrete pores dispersed within thecontinuous polymeric phase. The continuous polymeric phase also can bechemically crosslinked or elastomeric in nature.

The continuous polymeric phase of the porous particles generally has thesame chemical composition throughout that solid phase. That is, thecontinuous polymeric phase is generally uniform in chemical compositionincluding any components [for example, (e) opacifying colorant] that canbe incorporated therein. In addition, if mixtures of polymers composethe continuous polymeric phase, generally those mixtures also areuniformly distributed throughout.

As used in this disclosure, the term “isolated from each other” refersto the different (distinct) pores of the same or different sizes thatare separated from each other by some portion of the continuous solidphase and such discrete pores are not interconnected. Thus, “discrete”pores refer to “individual” or “closed” non-connected pores or voidsdistributed within the continuous polymeric phase.

The (a) porous particles can include “micro,” “meso,” and “macro”discrete pores, which according to the International Union of Pure andApplied Chemistry, are the classifications recommended for discrete poresizes of less than 2 nm, from 2 nm to and including 50 nm, and greaterthan 50 nm, respectively. Thus, while the (a) porous particles caninclude closed discrete pores of all sizes and shapes (that is, closed,non-interconnected discrete pores entirely within the continuouspolymeric phase) providing a suitable volume in each discrete pore,macro discrete pores are particularly useful. While there can be openmacro pores on the surface of the (a) porous particle, such open poresare not desirable for providing the advantages of the present invention,and may be present only by accident. The size of the (a) porousparticles, their formulation, and manufacturing conditions are theprimary controlling factors for discrete pore size. However, typicallythe discrete pores have an average size of at least 0.1 nm and up to andincluding 7,000 nm, or more likely at least 200 nm and up to andincluding 2,000 nm. Whatever the size of the discrete pores, they aregenerally distributed randomly throughout the continuous polymericphase. However, if desired, the discrete pores can be groupedpredominantly in one part (for example, in a “core” portion or in a“shell” portion) of the (a) porous particles.

Unless otherwise indicated, the term “non-porous” refers to particlesthat are not designed to have discrete pores or compartments within thesolid continuous polymeric phase and less than 20% of their total volumeconsists of pores.

“Opacity” is a measured parameter of an opacifying element according tothe present invention, which characterizes the extent to which thetransmission of electromagnetic radiation such as visible light isblocked. A greater opacity indicates a more efficient blocking (hiding)of electromagnetic radiation or higher light-blocking for the dry foamedopacifying layer.

Glass transition temperature of the organic polymers used to prepare thecontinuous polymeric phase, or (b) binder materials described below, canbe measured using Differential Scanning calorimetry (DSC) using knownprocedures. For many commercially available organic materials, the glasstransition temperatures are known from suppliers.

The terms “decorative fabric” and “non-woven fabric” are defined below.

The term “fabric” is meant to refer to a material composed of orprepared from naturally occurring fibers, synthetic fibers, or a mixtureof naturally occurring fibers and synthetic fibers of any desirablelength.

Uses

The method used according to this invention provides a laminatedlight-blocking decorative article of a desired weight, stiffness,opacity, color, and feel. These laminated light-blocking decorativearticles of this invention can have suitable light-blocking properties,feel, and color for use in various environments and structures. Suchlaminated light-blocking decorative articles of this invention may alsoexhibit improved sound and heat blocking properties. They can be usedas, for example, draperies and other window treatments, room dividers,cubicle curtains, banners, labels, coverings and tarpaulins (for examplefor vehicles, boats, and other objects), and packaging materials. Thelaminated light-blocking decorative articles can optionally have one ormore printable outer surfaces that are able to accept ink used in screenprinting, gravure printing, inkjet printing, thermal imaging (such as“dye sublimation thermal transfer”), or other imaging processes. Asdecorative surfaces go, the laminated light-blocking decorative articlesaccording to the present invention can have any type of decorativeimage, text, pattern, or combination thereof, as can be conceivablycreated by a person or machine.

For example, laminated light-blocking decorative articles can be awindow shades having blackout, feel, optional coloration, and otherproperties desired by the customer.

Non-Woven Fabrics

Each non-woven fabric used in the practice of the present invention hastwo opposing sides, that is a face side and a back side. These twoopposing sides can be the same or different in appearance, texture,feel, antimicrobial properties, or chemical composition, but the backside and face side labels are used to distinguish how the opacifyingelement is arranged in relation to the applied foamed opacifyingcomposition and decorative fabric as described in the text below.

For example, the non-woven fabric can be composed of a blended ornonblended fabric, and can be considered as spunlaced non-woven fabrics(or tanglefaced non-woven fabrics). Spunlaced non-woven fabrics aregenerally textile fabrics consisting of fibers entangled in apredetermined pattern to form a strong, unbonded structure. Thus, suchnon-woven fabrics can be typically in the form of fabrics composed offibers locked into place by fiber interaction, thereby providing acohesive structure without the need for chemical binders or fiberfusing.

Useful non-woven fabrics can be formed from naturally-occurring fibers,synthetic fibers, or mixtures of naturally-occurring fibers andsynthetic fibers. The commonly used fibers include naturally fibers suchas cotton, ramie, silk, linen, jute, flax, wool, and blends of suchnaturally-occurring fibers; synthetic fibers such as nylon, polyester,polypropylene, polyamide, rayon, and blends of such synthetic materials;and special fibers such as glass, carbon, nanofiber, bi-component, andsuperabsorbent fibers. Polyester fibers are particularly useful,especially for spunlaced non-woven fabrics. In additions, blends of oneor more naturally-occurring fibers and synthetic fibers can be used.

It is also possible that the non-woven fabrics are suitably tinted orcolored using dyes or pigments that would be readily apparent to oneskilled in this art in the fabric industry. Moreover, the non-wovenfabrics can have one or more printed pattern or images on the face side,and such patterns or images can be provided before or after laminationto the decorative fabric.

Useful non-woven fabrics can be obtained from various industrialsources, and the processes for making them are well known including theteachings in U.S. Pat. No. 3,748,217 (noted above), the disclosure ofwhich is incorporated herein by reference, especially with respect tothe teaching in Cols. 3 and 4 and the references cited therein.

Useful non-woven fabrics can have a basis weight (or “fabric weight”) ofat least 0.5 oz/yd² (or 16.95 g/m²), or at least 1 oz/yd (33.9 g/m²). Inother embodiments, the basis weight for non-woven fabrics used in thisinvention can up to and including 25 oz/yd² (or 847.7 g/m²), or up toand including 12.5 oz/yd² (423.9 g/m²).

Thus, in the practice of this invention, the various non-woven fabricsused in the practice of this invention can have the same or differentcolor, stiffness, textile, feel, chemical composition, or othermechanical or chemical properties. This is one of the main advantages ofthe present invention in that the various non-woven fabrics can bedifferent in any desired manner.

In many embodiments, the non-woven fabric can comprise a material thathas been treated in one or more ways to provide water-repellency orstain resistance, or both, particularly on its face side. For example,such treatments can comprise applying a suitable fluorochemical treatingagent, with or without a suitable antimicrobial agent (or biocide), toeither or both of the face and back sides of a non-woven fabric materialas well as to interstitial spaces within the non-woven fabric material,to provide a “treated” non-woven fabric, followed by suitable drying orcuring at elevated temperatures. A representative treatment process isdescribed in Cols. 4-6 of U.S. Pat. No. 6,884,491 (noted above) as wellin Cols. 6ff of U.S. Pat. No. 6,541,138 (Bullock et al.), thedisclosures of both of which are incorporated herein by reference. Thetreatment solutions can include one or more biocides (such asantimicrobials), crosslinking agents (including self-crosslinking latexpolymers), soil releasing agents, fire retardants, smoke suppressants,dispersants, thickeners, dyes, pigments, UV light stabilizers, and otheradditives that would be readily apparent to one skilled in the art. Suchtreatments can be particularly useful on the face side of the non-wovenfabric.

In general, suitable non-woven fabrics can have a dry average thicknessof at least 50 μm, and the thickness can depend upon various industrialand customer factors. This dry average thickness can be determined whenthe non-woven fabric comprises less than 5 weight % water (based on thetotal weight of the non-woven fabric) using the average of at least 3measurements taken at different places, or as determined using asuitable micrograph image.

Decorative Fabrics

Each decorative fabric used according to the present invention has twoopposing sides, that is a face side (usually a viewable or observer'sside) and a back side. These two opposing sides can be the same ordifferent in appearance, texture, feel, color or composition, but theback side and face side labels are used to distinguish how thedecorative fabric is arranged in relation to the non-woven fabric havingits back coated with a dry foamed aqueous opacifying composition. Theface side of such decorative fabrics can be any desired image, raisedtexture, “quilting”, or embossed design, printing, and thus generallyhave a decorative function. Means for providing this decorative functionare known in the art and include but are not limited to, decorativeweaving, printing using dye sublimation, screen or digital printing, andinkjet printing. Thus, decorative fabrics are generally woven fabricshaving decorative applied art and can be woven, patterned, embossed, orprinted. The ornamentation of such decorative fabrics can consist ofrepeated patterns and is achieved either by weaving, printing, orembroidering. For example, the decorative fabric can be a woven fabrichaving a repeating design pattern that is woven or embroidered into thedecorative fabric.

A decorative fabric can be in the form of woven or non-woven materialsthat are composed of naturally-occurring fibers, synthetic fibers, ormixtures of naturally-occurring fibers and synthetic fibers. Suitablenaturally-occurring fibers include but are not limited to, fibers ofcotton, linen, ramie, silk, wool, and others known in the natural world,and blends of fibers of such naturally-occurring materials. Suitablesynthetic fibers include but are not limited to, fibers of nylon,polyesters, acrylics, glass (fiberglass), polyurethanes, polyamides,polycarbonates, rayon, polyolefins, celluloses (include woven ornon-woven paper materials), acetates, aromatic polyamides, polyvinylchloride, and others known in the art, as well as combinations or blendsof any of these types of fibers, such as polyvinyl chloride coatedfibers of various materials. Useful fabrics also can be composed ofpolyvinyl chloride-clad polyester or polyvinyl chloride-clad fiberglass.Suitable fabric materials include but are not limited to, double clothjacquards (that is fabrics manufactured on a jacquard loom), brocades,dobby fabrics, prints, poplins, cross-dyes, crepes, and canvasses.

In some embodiments, the decorative fabric is a porous fabric comprisinga plurality of continuous yarn strands, all woven together, wherein eachyarn strand comprises a multifilament core that is coated with a coatingcomprising a thermoplastic polymer. Further details for such decorativefabrics and their use are provided in U.S. Patent ApplicationPublication 2018/0223474 (Nair et al.), the disclosure of which isincorporated herein by reference.

In many embodiments, the decorative fabric can comprise a material thathas been treated in one or more ways to provide water-repellency orstain resistance, or both, on either or both face and back sides. Forexample, such treatments can comprise applying a suitable fluorochemicaltreating agent, with or without a suitable antimicrobial agent (orbiocide), to the face side and back side of a decorative fabric materialas well as to interstitial spaces within the decorative fabric material,to provide a “treated” decorative fabric, followed by suitable drying orcuring at elevated temperatures. A representative treatment process isdescribed in Cols. 4-6 of U.S. Pat. No. 6,884,491 (noted above) as wellin Cols. 6ff of U.S. Pat. No. 6,541,138 (Bullock et al.), thedisclosures of both of which are incorporated herein by reference. Thetreatment solutions can include one or more biocides (such asantimicrobials), crosslinking agents (including self-crosslinking latexpolymers), soil releasing agents, fire retardants, smoke suppressants,dispersants, thickeners, dyes, pigments, UV light stabilizers, and otheradditives that would be readily apparent to one skilled in the art.

For example, a decorative fabric material can be treated with at leastone or more biocidal agents capable of destroying or preventing theactivity of bacteria, viruses, fungi, or mold, many of which materialsare known in the art, including antibiotics, trialkyl tin compounds,copper compounds, copper complexes of dehydroabietyl amine or8-hydroxyquinolinium 2-ethylhexoate, copper naphthenate, copper oleate,organosilicon quaternary ammonium compounds, silver metal and varioussilver salts.

One or more treatments of the decorative fabric material can be carriedout to achieve the desired properties while maintaining desired hand,feel, texture, drape, and aesthetic appearance.

In general, suitable decorative fabrics can have a dry average thicknessof at least 50 μm, and the thickness can depend upon the use of thelaminated decorative article and the type of decorative fabric materialsavailable for use. This dry average thickness can be determined when thedecorative fabric comprises less than 5 weight % water (based on thetotal weight of the decorative fabric) using the average of at least 3measurements taken at different places, or as determined using asuitable micrograph image.

The decorative fabric can also have an openness of at least 0% and up toand including 10%, or even at least 1% and up to and including 10%.“Openness” (Openness Factor, or OF) refers to how tight the weave is ina decorative fabric material, the percentage of holes in a fabricconstruction, and is sometimes referred to as “weave density.” The lowerthe OF, the less the light transmittance and the greater the visiblelight that is obstructed or blocked. It is the ratio between transparentand opaque surfaces and depends on the spacing and dimension of theyarn.

Aqueous Foamed Opacifying Compositions

Each aqueous foamed opacifying composition comprises five essentialcomponents (a), (b), (c), (d), and (e) as defined below that areessential for providing desired properties in a dry foamed opacifyinglayer used in the method of this invention.

The aqueous foamed opacifying composition generally has at least 35%solids and up to and including 70% solids, or more particularly at least40% solids and up to and including 60% solids.

(a) Porous Particles:

Porous particles used in the present invention containing discrete pores(or compartments or voids) are generally prepared using one or morewater-in-oil emulsions in combination with an aqueous suspensionprocess, such as in the Evaporative Limited Coalescence (ELC) processthat is known in the art. The details for the preparation of the porousparticles are provided, for example, in U.S. Pat. No. 8,110,628 (Nair etal.), U.S. Pat. No. 8,703,834 (Nair), U.S. Pat. No. 7,754,409 (Nair etal.), U.S. Pat. No. 7,887,984 (Nair et al.), U.S. Pat. No. 8,329,783(Nair et al.), and U.S. Pat. No. 8,252,414 (Putnam et al.), thedisclosures of all of which are incorporated herein by reference. Thus,the porous particles can be made by a multiple emulsion process thatprovides formation of individual porous particles comprising acontinuous polymer phase and multiple discrete internal pores, and suchindividual porous particle is dispersed in an external aqueous phase.The described Evaporative Limited Coalescence (ELC) process is used tocontrol the particle size and distribution while a hydrocolloid isincorporated to stabilize the inner emulsion of the multiple emulsionsthat provide the template for generating the discrete pores in theporous particles.

The (a) porous particles used in this invention generally have aporosity of at least 20 volume %, at least 35 volume %, or at least 40volume %, and up to and including 60 volume %, up to and including 65volume %, or up to and including 70 volume %, all based on the totalporous particle volume. Porosity can be measured by an obviousmodification of the known mercury intrusion technique. Except as notedbelow, the volume of each discrete pore is essentially full of air withperhaps some non-evaporated water present.

Thus, the (a) porous particles are generally polymeric and organic innature (that is, the continuous polymeric phase is polymeric and organicin nature) and non-porous particles (having less than 20% porosity) areexcluded from use in the present invention. Inorganic particles can bepresent on the outer surface of each porous particle if desired.

The (a) porous particles can be composed of a continuous polymeric phasederived from one or more organic polymers that are chosen so that thecontinuous polymeric phase has a glass transition temperature (T_(g)) ofat least 25° C., or more typically of at least 25° C. and up to andincluding 180° C., as determined using Differential Scanningcalorimetry.

The continuous polymeric phase can comprise one or more organic polymershaving the properties noted above, in an amount of at least 70 weight %and up to and including 100 weight % based on the total polymer weightin the continuous polymeric phase. In some embodiments, the continuouspolymeric phase is composed of one or more cellulose polymers (orcellulosic polymers) including but not limited to, those cellulosicpolymers derived from one or more of cellulose acetate, cellulosebutyrate, cellulose acetate butyrate, and cellulose acetate propionate.Mixtures of these cellulose polymers can also be used if desired, andmixtures comprising a polymer derived from cellulose acetate butyrate asat least 80 weight % of the total of cellulose polymers (or of allpolymers in the continuous polymeric phase) are particularly usefulmixtures. Details about such polymers are provided, for example, in U.S.Pat. No. 9,963,569 (Nair et al.), the disclosure of which isincorporated herein by reference.

In other embodiments, the continuous polymeric phase can comprise one ormore organic polymers such as polyesters, styrenic polymers (for examplepolystyrene and polychlorostyrene), mono-olefin polymers (for example,polymers formed from one or more of ethylene, propylene, butylene, andisoprene), vinyl ester polymers (for example, polymer formed from one ormore of vinyl acetate, vinyl propionate, vinyl benzoate, and vinylbutyrate), polymers formed from one or more α-methylene aliphaticmonocarboxylic acid esters (for example, polymers formed from one ormore of methyl acrylate, ethyl acrylate, butyl acrylate, dodecylacrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethylmethacrylate, butyl methacrylate, and dodecyl methacrylate), vinyl etherpolymers (such as polymers formed from one or more of vinyl methylether, vinyl ethyl ether, and vinyl butyl ether), and vinyl ketonepolymers (for example, polymers formed from one or more of vinyl methylketone, vinyl hexyl ketone, and vinyl isopropenyl ketone). Other usefulpolymers include polyurethanes, urethane acrylic copolymers, epoxyresins, silicone resins, polyamide resins, and polyesters of aromatic oraliphatic polycarboxylic acids with one or more aliphatic diols, such aspolyesters of isophthalic or terephthalic or fumaric acid with diolssuch as ethylene glycol, cyclohexane dimethanol, and bisphenol adductsof ethylene or propylene oxides. The polyesters can be saturated orunsaturated. Other useful polyesters include lactic acid polymers,glycolic acid polymers, caprolactone polymers, and hydroxybutyric acidpolymers. Details of such useful polymers are provided, for example inU.S. Pat. No. 9,891,350 (Lofftus et al.) and U.S. Pat. No. 9,469,738(Nair et al.), the disclosures of both of which are incorporated hereinby reference.

The continuous polymeric binder of the (a) porous particles can also bederived from ethylenically unsaturated polymerizable monomers andpolyfunctional reactive compounds as described for example in U.S. Pat.No. 8,703,834 (noted above), the disclosure of which is incorporatedherein by reference.

In some embodiments, the continuous polymeric phase of the (a) porousparticles comprises one or more cellulose polymers, a polyester, apolystyrene, or a combination thereof.

In general, the (a) porous particles used in the present invention havea mode particle size equal to or less than 50 μm, or of at least 2 μmand up to and including 50 μm, or typically of at least 3 μm and up toand including 30 μm or even up to and including 40 μm. Most useful (a)porous particles have a mode particle size of at least 3 μm and up toand including 20 μm. Mode particle size represents the most frequentlyoccurring diameter for spherical particles and the most frequentlyoccurring largest diameter for the non-spherical particles in a particlesize distribution histogram, which can be determined using knownequipment (including light scattering equipment such as the Sysmex FPIA3000 Flow Particle Image Analyzer that used image analysis measurementsand that can be obtained from various sources including MalvernPanalytical; and coulter counters and other particle characterizingequipment available from Beckman Coulter Diagnostics), software, andprocedures.

Pore stabilizing materials such as hydrocolloids can be present withinat least part of the volume of the discrete pores distributed throughoutthe continuous polymeric phase, which pore stabilizing materials aredescribed in the Nair, Nair et al., and Putnam et al. patents citedabove. For example, the pore stabilizing hydrocolloids can be selectedfrom the group consisting of carboxymethyl cellulose (CMC), a gelatin orgelatin derivative, a protein or protein derivative, polyvinyl alcoholand its derivatives, a hydrophilic synthetic polymer, and awater-soluble microgel.

It can be desired in some embodiments to provide additional stability ofone or more discrete pores in the (a) porous particles during theirformation, by having one or more amphiphilic block copolymers disposedat the interface of the one or more discrete pores and the continuouspolymeric phase. Such materials are “low HLB”, meaning that they have anHLB (hydrophilic-lipophilic balance) value as it is calculated usingknown science, of 6 or less, or even 5 or less. The details of theseamphiphilic polymers and their use in the preparation of the (a) porousparticles are provided in U.S. Pat. No. 9,029,431 (Nair et al.), thedisclosure of which is incorporated herein by reference. A particularlyuseful amphiphilic block copolymer useful in such embodiments comprisespoly(ethyleneoxide) and poly(caprolactone) that can be represented asPEO-b-PCL. Amphiphilic block copolymers, graft copolymers and randomgraft copolymers containing similar components are also useful includingother polymeric emulsifiers such as GRINDSTED® PGPR 90, polyglycerolpolyricinolate emulsifier, obtained from Danisco, Dupont.

Such an amphiphilic copolymer can be generally present in the (a) porousparticles in an amount of at least 1 weight %, or at least 2 weight %and up to and including 50 weight %, based on total (a) porous particledry weight.

The (a) porous particles used in this invention can be spherical ornon-spherical depending upon the desired use. In a method used toprepare the (a) porous particles, additives (shape control agents) canbe incorporated into the first or second aqueous phases, or in the oil(organic) phase to modify the shape, aspect ratio, or morphology of the(a) porous particles, using known technology. The (a) porous particlescan also comprise surface stabilizing agents, such as colloidal silica,on the outer surface in an amount of at least 0.1 weight %, based on thetotal dry weight of the (a) porous particle.

The average size of the discrete pores in the (a) porous particles isdescribed above.

The (a) porous particles can be provided as powders, or as aqueoussuspensions (including water or water with water-miscible organicsolvents such as alcohols). Such powders and aqueous suspensions canalso include surfactants or suspending agents to keep the (a) porousparticles suspended or for rewetting them in an aqueous medium.

The (a) porous particles are generally present in a dry foamedopacifying composition in an amount of at least 0.1 weight % and up toand including 35 weight %, or typically at least 0.5 weight % and up toand including 25 weight %, or even at least 1 weight % and up to andincluding 20 weight %, based on the total weight of the dry foamedopacifying composition (including any residual aqueous medium),particularly when the (a) porous particles have a mode size of at least3 μm and up to and including 20 μm.

In the dry foamed opacifying composition, the large mismatch inrefractive index between the discrete pores of the (a) porous particlesand the polymer walls (continuous polymeric phase), causes incidentelectromagnetic radiation passing through the dry foamed opacifyingcomposition to be scattered by the multiplicity of interfaces anddiscrete pores. The back scattered electromagnetic radiation can againbe scattered and returned in the direction of the incidentelectromagnetic radiation thus reducing the attenuation and contributingto the opacifying power and brightness or luminous reflectance of thedry opacifying layer. If a small amount of (e) opacifying colorant ispresent in the (a) porous particles, for example either in the discretepores or in the continuous polymer phase of the (a) porous particles,the opacifying power of the dry foamed opacifying composition isincreased. This is because the multiple scattering of electromagneticradiation in the dry foamed opacifying composition increases the pathlength of the electromagnetic radiation through it, thereby increasingthe chance that the electromagnetic radiation will encounter the (e)opacifying colorant and be blocked or absorbed by it.

(b) Binder Materials:

The aqueous foamed opacifying composition also contains one or more (b)binder materials to hold the (a) porous particles, (c) two or moreadditives, and (e) opacifying colorant together on the non-woven fabricafter the composition has been applied thereto. The one or more (b)binder materials can behave as a binding matrix for all the materials insuch wet compositions, and can form a (b′) matrix material to hold the(a) porous particles, (c) one or more additive, and (e) opacifyingcolorant(s) together in a dry foamed opacifying composition.

It is particularly useful that a (b) binder material have the followingproperties: (i) it is water-soluble or water-dispersible; (ii) it iscapable of being disposed onto a suitable substrate as described below;(iii) it is capable of being dried and at least partially crosslinked(or at least partially cured); (iv) it has good light and heatstability; and (v) it is film-forming but contributes to the flexibilityof the laminate precursor (and later laminated decorative article) andis thus not too brittle, for example generally having a glass transitiontemperature (T_(g)) of less than 25° C., or of less than 0° C., or ofless than or equal to −10° C., or of less than or equal to −25° C., asdetermined using Differential Scanning calorimetry.

The choice of (b) binder materials can also be used to optimize a (b′)matrix material in the dry formulation of all of the (a), (c), and (e)materials described herein, to provide desired properties. For example,the (b) binder material can be used to provide a (b′) matrix materialthat adds to a supple feel to touch and a flexibility desired, forexample, for hanging draperies. The (b′) matrix material derived fromthe (b) binder material upon its at least partial and possibly, fullcuring or crosslinking.

The (b) binder material can include one or more organic polymers thatare film forming and that can be provided as an emulsion, dispersion, orin an aqueous solution, and that cumulatively provide the propertiesnoted above. It can also include one or more polymers that areself-crosslinking or self-curable, or it can include one or morepolymers to which crosslinking agents are added and are thus curable orcapable of being at least partially crosslinked under appropriateconditions.

For example, if the (b) binder material comprises a crosslinkable (orcurable) polymer in the presence of a suitable crosslinking or curableagent or catalyst, such crosslinking (or curing) can be activatedchemically with heat, radiation, or other known means. A curing orcrosslinking process serves to provide improved insolubility of theresulting dry opacifying layer as well as cohesive strength and adhesionto the substrate. The curing or crosslinking agent is generally achemical having functional groups capable of reacting with reactivesites in a (b) binder material (such as a functionalized latex polymer)under curing conditions to thereby produce a crosslinked structure.Representative crosslinking agents include but are not limited to,multi-functional aziridines, aldehydes, methylol derivatives, andepoxides.

Useful (b) binder materials include but are not limited, to poly(vinylalcohol), poly(vinyl pyrrolidone), ethylene oxide polymers,polyurethanes, urethane-acrylic copolymers, other acrylic polymers,styrene-acrylic copolymers, vinyl polymers, styrene-butadienecopolymers, acrylonitrile copolymers, and polyesters, silicone polymersor a combination of two or more of these organic polymers. Such (b)binder materials are readily available from various commercial sourcesor they can be prepared using known starting materials and syntheticconditions. The (b) binder material can be anionic, cationic or nonionicin total charge. A useful class of film-forming (b) materials includesaqueous latex polymer dispersions such as acrylic latexes that can beionic or nonionic colloidal dispersions of acrylate polymers andcopolymers. Useful film-forming aqueous latexes includestyrene-butadiene latexes, poly(vinyl chloride) and poly(vinylidenechloride) latexes, poly(vinyl pyridine) latexes, poly(acrylonitrile)latexes, and latexes formed from acrylonitrile, butyl acrylate, andethyl acrylate.

The one or more (b′) matrix materials derived from one or more (b)binder materials, can be present in the dry foamed opacifyingcomposition in an amount of at least 10 weight % and up to and including80 weight %, or typically at least 20 weight % and up to and including60 weight %, based on the total dry foamed opacifying composition (thatis, the total weight of all components including any residual solvent).

It is useful that the dry weight ratio of the (a) porous particles tothe (b′) matrix material in the dry foamed opacifying composition is atleast 2:3 and up to and including 9:1, and more likely at least 1:1 andup to and including 3:1.

(c) Two or More Additives:

The dry foamed opacifying composition used in the present invention canfurther include (c) two or more additives in an amount of at least0.0001 weight % and up to and including 50 weight % and typically atleast 1 weight % and up to and including 45 weight %, based on the totalweight of the dry foamed opacifying composition (including any residualaqueous medium). These amounts refer to the total amounts of the (c) twoor more additives, not to each additive individually.

Such (c) one or more additives include materials such as dispersants,foaming surfactants, foam stabilizers, plasticizers, fire retardants,biocides (such as fungicides and antimicrobials), preservatives,thickeners, pH buffers, thickeners, and inert inorganic and organicfillers that are not inorganic or organic pigments (colorants). Thenoted amounts refer to the total of all (c) two or more additives. Therecan be mixtures of each type of (c) two or more additives or mixtures oftwo or more types of (c) two or more additives in each dry opacifyinglayer. It is particularly useful in most dry foamed opacifyingcompositions to include at least one foaming surfactant and at least onefoam stabilizer, and representative materials are defined below.

Such (c) two or more additives are different from the (e) opacifyingcolorants (described below) because individually or collectively, theywill not substantially block or absorb incident electromagneticradiation in the wavelength range of at least 380 nm and up to andincluding 800 nm, as determined in the manner described above for the(e) opacifying colorant.

Any of these (c) two or more additives thereof can be present within anylocation of the dry foamed opacifying composition, including but notlimited to: the continuous polymeric phase of the (a) porous particles;a volume of some or all the discrete pores of the (a) porous particles;or both the volume of the discrete pores and the continuous polymericphase of the (a) porous particles. Alternatively, such (c) two or moreadditives can be present in the (b) binder material alone, or in boththe (b) binder material and in the (a) porous particles.

It would also be understood that while such (c) two or more additivescan be in the dry foamed opacifying composition, and the same ordifferent (c) two or more additives can be also present in the non-wovenfabric or decorative fabric as described above.

The “inert” inorganic or organic fillers useful as (c) two or moreadditives are particles that can be added to reduce the amount of (b)binder materials. Such inert materials do not undergo a chemicalreaction in the presence of water or other components in an aqueousfoamed opacifying composition (described below); nor do they absorbelectromagnetic radiation like the (e) opacifying colorants. Usefulinert organic or inorganic filler materials include but are not limitedto titanium dioxide, talc, clay (for example, kaolin), magnesiumhydroxides, aluminum hydroxides, dolomite, glass beads, silica, mica,glass fibers, nano-fillers, calcium carbonate, and combinations thereof.

At least one of the (c) two or more additives is a surfactant that isdefined as a compound that reduces surface tension in an aqueousformulation composition. In most embodiments, this essential surfactantis a foaming agent that functions to create and enhance foam formation.The (c) two more additives comprise one or more foaming agents as wellas one or more foam stabilizing agents (or foam stabilizers) that arealso surface active agents that function to structure and stabilize thefoam. Examples of useful foaming agents (foaming surfactants) that arealso surface-active agents, and foam stabilizers, include but are notlimited to, ammonium stearate, ammonium palmitate, sodium laurylsulfate, ammonium lauryl sulfate, ammonium or sodium alkylsulfosuccinate, disodium stearyl sulfosuccinate, diammonium n-octadecylsulfosuccinamate, ethoxylated alcohols, ionic or nonionic agents such asfatty acid soaps or a fatty acid condensation product with an alkalineoxide, for example, the condensation product of ethylene oxide withlauryl or oleic acid or an ester of fatty acids and similar materials,many of which can be obtained from various commercial sources. Mixturesof foaming agents can be used if desired, and mixtures of foamstabilizers can be used. Some of the noted compounds also act as foamstabilizers, but it best to use a separate foaming surfactant (agent)and a separate foam stabilizer together for synergistic effects offoaming and stabilization.

The relative amounts of each of the foaming surfactants and foamstabilizers is not critical as long as the desired functions areevident, that is suitable foaming properties as required to prepare anaqueous foamed opacifying composition, and stability of that aqueousfoamed opacifying composition during storage and manufacture of thelaminate precursors described herein. The optimal amounts of each ofthese (c) two or more additives can be determined by using routineexperimentation and the teaching provided herein.

Useful biocides (that is, antimicrobial agents and antifungal agents)that can be present as (c) two or more additives and can include but arenot limited to, silver particles, platelets, or fibrous strands, andsilver-containing compounds such as silver chelates and silver saltssuch as silver sulfate, silver nitrate, silver chloride, silver bromide,silver iodide, silver iodate, silver bromate, silver tungstate, silverphosphate, and silver carboxylates. In addition, copper particles,platelets, or fibrous strands and copper-containing compounds such ascopper chelates and copper salts can be present as (c) two or moreadditives for biocidal purposes.

It can also be useful to include thickeners as (c) two or more additivesin order to modify the viscosity of the aqueous foamed opacifyingcomposition and to control its rheology.

In some embodiments, the (c) two or more additives further comprises oneor more of an antimicrobial agent, a fire retardant, or both anantimicrobial agent and a fire retardant.

(d) Aqueous Medium:

Water is the predominant solvent used as an (d) aqueous medium in theaqueous foamed opacifying compositions. By “predominant” is meant thatof the total weight of solvents in the (d) aqueous medium, watercomprises at least 75 weight %, and more likely at least 80 weight % andup to and including 100 weight %, of the total solvent weight. Auxiliarysolvents that can be present must not adversely affect or harm the othercomponents in the aqueous formulation. Such auxiliary solvents can bewater-miscible organic solvents such as alcohols and ketones.

(e) Opacifying Colorants:

The use of (e) opacifying colorants in a dry foamed opacifyingcomposition is desirable to block or absorb incident electromagneticradiation within the range of wavelengths of at least 380 nm and up toand including 800 nm. The (e) opacifying colorants can be water-solubledyes or water-dispersible pigments, or combinations of each or bothtypes of materials. The amount of electromagnetic radiation that can beblocked or absorbed by an (e) opacifying colorant can be determined bymeasuring opacity of an applied composition as described below. The (e)opacifying colorant can be a single colorant or a combination ofmaterials that collectively act as the “opacifying colorant.”

In many embodiments, the (e) opacifying colorant can be present withinthe (a) porous particles, for example, within a volume of at least some,if not all, discrete pores within the (a) porous particles orincorporated within the continuous polymeric binder of the (a) porousparticles, or within both the volume of discrete pores and thecontinuous polymeric binder of the (a) porous particles. This is highlyadvantageous as the (a) porous particles can be used to “encapsulate”various (e) opacifying colorants as well as some or all of the (c) twoor more additives (described below) so they are kept isolated from theother components of the dry foamed opacifying composition. For example,the (e) opacifying colorant can be located solely within the (a) porousparticles. In other embodiments, it can be useful to incorporate (e)opacifying agents solely or additionally within the (b) binder materialin which the (a) porous particles are dispersed.

While the (e) opacifying colorants can provide some coloration ordesired hue, they are not purposely chosen for this purpose and are thusmaterials that are chosen to be different from the tinting colorantsdescribed above for the (c) two or more additives.

Examples of (e) opacifying colorants that can be used individually or incombination include but are not limited to, neutral or black pigments ordyes (other than a carbon black), carbon black, black iron oxide,graphite, aniline black, anthraquinone black, or combinations thereof,as well as combinations of colored pigments or dyes such as cyan,magenta, yellow, green, orange, blue, red and, violet dyes. The presentinvention is not limited to only the specific (e) opacifying colorantsdescribed herein but these are considered as suitable guidance for askilled worker to devise other combinations of (e) opacifying colorantsfor the desired absorption in a chosen range of electromagneticradiation. A carbon black or neutral or black pigment or dye other thana carbon black, of which there are many types available from commercialsources, is particularly useful as an (e) opacifying colorant.

The (e) opacifying colorant can be generally present in the dry aqueousfoamed opacifying composition in an amount of at least 0.002 weight %and up to and including 2 weight %, or even at least 0.02 weight % andup to and including 1 weight %, all based on the total weight of the dryfoamed opacifying composition (including any aqueous medium). Asmixtures of the materials can be used if desired, these amounts alsorefer to the total amount of a mixture of materials used as the (e)opacifying colorant. As noted above, an (e) opacifying colorant cancomprise a combination of two or more component materials (such as acombination of dyes or a combination of pigments) designed in hues andamounts so that the combination meets the desired black-out andcoloration properties described herein.

In some embodiments, the (e) opacifying colorants, if in pigment form,are generally milled to a fine particle size and then encapsulatedwithin the volume of the discrete pores of the (a) porous particles byincorporating the milled pigment within an aqueous phase used in makingthe (a) porous particles. Alternatively, the (e) opacifying colorant canbe incorporated within the continuous polymeric phase of the (a) porousparticles by incorporating the (e) opacifying colorant in the oil phaseused in making the (a) porous particles. Such arrangements can beachieved during the manufacture of the (a) porous particles using theteaching provided herein and the teaching provided in references citedabove for making the (a) porous particles.

In some embodiments, it can be useful to incorporate at least 95% (byweight) of the total (e) opacifying colorant within the volume of the(a) porous particles (either in the discrete pores, continuous polymericphase, or both), and to incorporate the remainder, if any, within the(b) binder material. However, in many other embodiments, 100% of the (e)opacifying colorant is incorporated within the (a) porous particles. Forexample, more than 50% of the total (e) opacifying colorant can bedisposed or incorporated within the continuous polymeric phase of the(a) porous particles, and the remainder can be incorporated within thevolume of the discrete pores. Alternatively, all the (e) opacifyingcolorant can be incorporated into the volume of the discrete pores.

In all embodiments, the (e) opacifying colorants are different materialsfrom the (a) porous particles, (b) binder materials, and (c) two or moreadditives described herein.

Aqueous Foamable Opacifying Compositions

The dry foamed opacifying compositions formed according to the presentinvention can be provided from corresponding aqueous foamed opacifyingcompositions that can be prepared using the materials and proceduresdescribed below.

The essential (a) through (e) components described above are generallypresent in an (d) aqueous medium in amounts different from the amountsdefined above for the dry foamed opacifying layer. However, the relativepercentages (proportions) of the (a) through (c) and (e) components inthe aqueous foamed opacifying composition generally should be the sameas in the dry foamed opacifying layer.

The amounts of the (a) through (e) components in the aqueous foamableopacifying composition and the aqueous foamed opacifying composition areessentially the same as foaming does not appreciably change the % solidsor amounts of each components.

For example, the (a) porous particles (as described above) can bepresent in an aqueous foamed opacifying composition in an amount of atleast 0.05 weight % and up to and including 20 weight %, or typically ofat least 0.5 weight % and up to and including 15 weight %, all based onthe total weight of the aqueous foamed opacifying composition. Such (a)porous particles generally have a mode particle size of at least 2 μmand up to and including 50 μm and a porosity of at least 20 volume % andup to and including 70 volume %.

One or more (b) binder materials (as described above) can be present inthe aqueous foamed opacifying composition in an amount of at least 15weight % and up to and including 70 weight % or typically of at least 30weight % and up to and including 50 weight %, all based on the totalweight of the aqueous foamed opacifying composition.

The (c) two or more additives (as described above) can be present in theaqueous foamed opacifying composition in an amount of at least 0.0001weight % and up to and including 30 weight % or typically of at least0.001 weight % and up to and including 20 weight %, all based on thetotal weight of the aqueous foamed opacifying composition. At least oneof such (c) two or more additives is a foaming surfactant (as describedabove) and another is a foam stabilizer (as described above). Theseamounts refer to the total amounts of the (c) two or more additives, notto each additive individually.

The one or more (e) opacifying colorants (as described above) can bepresent in the aqueous foamed opacifying composition in an amount of atleast 0.0001 weight % or at least 0.003 weight % and up to and including0.5 weight %, or even in an amount of least 0.001 weight % and up to andincluding 0.3 weight % especially when the opacifying colorant is acarbon black, all based on the total weight of the aqueous foamedopacifying composition.

Water is the predominant solvent used in an (d) aqueous medium in theaqueous formulations. By “predominant” is meant that of the total weightof solvents in the (d) aqueous medium, water comprises at least 75weight %, and more likely at least 80 weight % and up to and including100 weight %, of the total solvent weight. Auxiliary solvents that canbe present must not adversely affect or harm the other components in theaqueous formulation. Such auxiliary solvents can be water-miscibleorganic solvents such as alcohols and ketones.

The aqueous medium can comprise at least 30 weight % and up to andincluding 70 weight %, or typically at least 40 weight % and up to andincluding 60 weight %, of the total aqueous foamed opacifyingcomposition weight. Or, the foamed aqueous

All (a), (b), (c), and (e) components can be suitably mixed in an (d)aqueous medium by dispersing with a cowles blade. Representative timeand temperature conditions for making such aqueous foamed opacifyingcompositions would be readily apparent to one skilled in the art.

Making Laminated Light-Blocking Decorative Articles

According to the present invention, a non-woven fabric having a faceside and back side can be independently provided (step A) as describedabove. The face side is considered the side of the non-woven fabric thatis viewable and left uncovered. A skilled worker can decide which “side”is best for application of the aqueous foamed opacifying composition.For example, the worker may choose the back side as the lessaesthetically appealing side of the non-woven fabric and then theopposing side that has the nicer touch or color may be chosen as theface side.

The dry foamed opacifying layer typically comprises (a) porousparticles, a (b′) matrix material, (c) two or more additives, an (e)opacifying colorant, and possibly some residual (d) aqueous medium, allof which are described in more detail above.

Previously to or in combination with step A) according to the presentinvention, an aqueous foamed opacifying composition can be formed byappropriate foaming or aerating a corresponding aqueous foamableopacifying composition that has basically the same materials andcomponent concentration.

Thus, the aqueous foamable opacifying composition can be aerated toprovide an aqueous foamed opacifying composition having a foam densityof at least 0.1 g/cm³ and up to and including 0.5 g/cm³, or of at least0.15 g/cm³ and up to and including 0.4 g/cm³, or even of at least 0.15g/cm³ and up to and including 0.27 g/cm³. This aeration procedure can becarried out using suitable conditions and equipment that would bereadily apparent to one skilled in the art in order to create a “foam,”for example in the presence of a foaming surfactant and foam stabilizerthat are present at least in the (c) two or more additives describedabove. For example, aeration can be carried out by mechanicallyintroducing air or an inert gas (such as nitrogen or argon) in acontrolled manner. High shear mechanical aeration can be carried outusing sonication or high-speed mixers, such as those equipped with acowles blade, or with commercially available rotorstator mixers withinterdigitated pins such as an Oakes mixer or a Hobart mixer, byintroducing air under pressure or by drawing atmospheric air into theaqueous foamable opacifying composition with the whipping action of themixer. Suitable foaming equipment can be used in a manner to provide thedesired foam density with modest experimentation. It can be useful tochill or cool the aqueous foamable opacifying composition below ambienttemperature to increase stability by increasing composition viscosity,and to prevent its collapse. This chilling operation can be carried outimmediately before, immediately after, or during the aeration procedure.Stability of the resulting aqueous foamed opacifying composition canalso be enhanced by the presence of a foam stabilizing agent as one ofthe (c) two or more additives.

Onto the back side of the non-woven fabric, an aqueous foamed opacifyingcomposition described above can be applied (step B) to provide anapplied coating or layer of that aqueous foamed opacifying composition.The wet coverage of the applied aqueous foamed opacifying compositionscan be any desired amount, that upon drying, can provide a dry coverageas described below.

The aqueous foamed opacifying composition can be applied using asuitable application means and in any suitable manner. For example, thenon-woven fabric can be coated with an aqueous foamed opacifyingcomposition using a floating knife, hopper, blade, or gap coatingapparatus and appropriate coating procedures including but not limitedto blade coating, gap coating such as “knife-over-roll” and“knife-over-table” operation, floating knife, slot die coating, or slidehopper coating. For example, the aqueous foamed opacifying compositioncan be disposed directly onto a back side of the non-woven fabricwherein “directly” means there are no intervening or intermediatelayers, or it can be disposed indirectly onto the back side of thenon-woven fabric, meaning that an interlayer of some type (primer oradhesive layer) can be present.

The applied aqueous foamed opacifying composition can be dried (step C)to provide a dry coverage of less than or equal to 1000 g/m², andgenerally at least 50 g/m², or at least 100 g/m² and up to and including500 g/m² of a dry foamed opacifying composition having a light blockingvalue (LBV_(oc)) of at least 2, or at least 3. In reference to a dryfoamed opacifying layer, the term “dry” means that the layer comprisesthe aqueous medium (described below) in an amount of less than 5 weight%, or even less than 2 weight %, based on the total weight of the dryfoamed opacifying layer. Drying operations to remove most or all of theaqueous medium can be achieved using suitable apparatus and treatmentswith heat or radiation that does not adversely affect the non-wovenfabric and the aqueous foamed opacifying composition. For example,drying can be accomplished by heating with warm or hot air, microwaves,or IR irradiation at a temperature and time sufficient for drying (forexample, at least 160° C.) to provide a dry foamed opacifying layer.

A decorative fabric having a face side and a back side is provided (stepD) and its back side is brought into lamination contact (step E) withthe dry foamed opacifying layer that has been applied and dried on thenon-woven fabric. The E) laminating step includes at least partial anddesirably sufficient curing of the dry foamed opacifying layer. This canbe facilitated by the presence in the applied aqueous foamed opacifyingcomposition of curable or crosslinkable polymers as (b) binder materialsand appropriate catalysts to form the (b′) matrix material. For example,a curing or crosslinking reaction can occur between reactive side groupsof suitable curable polymer chains in a functionalized self-crosslinkinglatex composition to form (b′) matrix material from the (b) bindermaterial. If the chosen (b) binder material is not itself heat reactive,suitable catalysts and curing (crosslinking) agents can be added topromote curing or crosslinking.

One suitable technique for lamination includes the use of an optionaladhesive material such as a thin intermediate heat seal or cold sealadhesive material between the decorative fabric back side and the dryfoamed opacifying composition disposed on the non-woven fabric. In someembodiments, the adhesive material is incorporated within the dry foamedopacifying layer.

When using a heat seal adhesive, the non-woven fabric with the dryfoamed opacifying composition can be supplied in web or sheet form inthe manufacturing operation; the heat seal adhesive can be applied toone of the surfaces to be adhered; and then the back side of thedecorative fabric is laminated thereto. Alternatively, or additionally,the heat seal adhesive can be supplied to the back side of thedecorative fabric and the two articles are brought together duringlamination. The heat seal adhesive also can be supplied (sprayed orsquirted) between the two articles as they are brought together. Theheat seal adhesive, after being heated, is then allowed to cool forexample to room temperature, followed by lamination of the two articles.

Suitable adhesive materials are known in the art, and can comprise atleast one polyamide, polyester, epoxy resin, acrylic resin, anhydridemodified polyolefin, polyurethane, or blends of two or more types ofpolymers.

Other adhesive materials can be used in the present invention includingbut not limited to use of a layer of any cold seal orpressure-sensitive, photosensitive, or thermally-sensitive adhesiveprecursor material, followed by “activation” to create an adhesive layerusing pressure, photo exposure, or thermal exposure, respectively. Forexample, liquid adhesives can be used including plastisol, epoxy,acrylic, organosol, and urethane adhesives that can be applied to eitherthe dry foamed opacifying layer or the decorative fabric with a suitablecoating technique (gravure cylinder, knife, roller, reverse roller, oranilox roller) under heat, followed by cooling to secure the adhesivebond.

It is also possible to laminate the dry foamed opacifying layer and thedecorative fabric without the use of an intermediate adhesive layer.This can be done in any suitable manner known in the art usingmechanical means without an adhesive means, using for example, directcalendar lamination to form a mechanical bond between the two articles.In direct calendar lamination, the two articles are brought together forexample, under heat from appropriate sources (for example, individualsupply rolls) and fed together into pressure rollers or a combination ofcalendar and embossing rollers to form the mechanical bonding uponcooling. The resulting laminated light-blocking decorative article canthen be taken up into a roll or otherwise stored or immediately used infinishing operations.

Subsequent to or simultaneously with the E) laminating step, the dryfoamed opacifying layer is densified (or crushed), in step F) so that itwill have a thickness that is at least 20% less than its thicknessbefore densifying in the resulting laminated light-blocking decorativearticle. Densification or crushing is a process of subjecting the dryfoamed opacifying composition to mechanical pressure, to densify (reducefoamed volume) and to reduce layer thickness. This process can becarried out in any suitable manner but it is generally carried out by aprocess that provides pressure to the dry foamed opacifying layer in theintermediate “laminate”, for example, by passing it through acompression calendering operation, pressing operation, or embossingoperation, or a combination thereof. For example, the intermediatelaminate can be pressed between flat plates or through nip rollers underpressure, or it can be passed through a combination of calendering andembossing rollers to reduce the thickness of the dry foamed opacifyinglayer and to densify the foam structure therein. This process can beconsidered a “densifying operation” as the dry foamed opacifying layeris made denser while it is pressed together. The thickness of the dryfoamed opacifying layer before and after crushing (densifying) can bedetermined by a known technique such as laser profilometry.

The crushing or densifying operation can be carried out at any suitabletemperature including room temperature (for example, 20-25° C.) and upto and including 150° C., or more likely at a temperature of at least20° C. and up to and including 150° C., or at least 50° C. and up to andincluding 120° C. The crushing or densifying operation can be carriedout at nip pressures that are suitable for the construction of thelaminated light-blocking article including the openness factor toprevent over crushing and consequent loss of uniform opacity of the dryfoamed opacifying layer. A useful crushing pressure can be determinedusing routine experimentation depending upon several factors includingthe dry foamed opacifying layer and type and weight of non-woven fabricused. For example, a useful crushing or densification pressure can be atleast 5 psi (34.5 kPa) and up to and including 200 psi (1379 kPa).

Once densification is completed, each laminated light-blockingdecorative article can be used immediately or stored for lateradditional finishing operations that would be readily apparent to oneskilled in the art, some of which are described below.

Alternatively or additionally, the face side of the non-woven fabric canbe modified with embossing or printing to provide a suitable image orpattern using known procedures such as inkjet printing or flexographicprinting, thereby forming printed images of text, pictures, symbols, orcombinations thereof. Such printed images can be visible, or they caninvisible to the unaided eye (for example, using fluorescent dyes in theprinted images). Alternatively, an outer surface can be covered bysuitable means with a colorless continuous or discontinuous layer toprovide a protective finish, or anti-microbial or soil releaseproperties. In many instances, the image formed in this manner, forexample, on an outer surface, is not visible or discernible from theother outer surface of the laminated light-blocking decorative article.In many instances, the image formed in this manner, for example, on oneouter surface, is not visible or discernible from the other outersurface of the laminated light-blocking decorative article.

A thermally printed image can be formed on the face side of thenon-woven fabric or on the face side of the decorative fabric, forexample, by using a thermal (sublimable) dye transfer printing process(using heat and with or without pressure) from one or more thermal donorelements comprising a dye donor layer comprising one or more dyesublimation printable colorants. For example, a thermal colorant imagecan be obtained using one or more thermal dye patches (areas) with orwithout a thermal colorless (clear) patch (area). Useful details of sucha process are provided in U.S. Patent Application Publication2018/0327965 (Herrick et al.), the disclosure of which is incorporatedherein by reference.

In some embodiments, the laminated light-blocking decorative articleprepared according to this invention can be a blackout draperyexhibiting a stiffness of less than 15 mN, as measured using a L&Wbending force test and an L&W Bending Tester apparatus (Lorentzen andWettre Products).

In other embodiments, a laminated light-blocking decorative articleaccording to this invention can be a blackout shade fabric exhibiting astiffness of at least 15 mN, as measured by L&W bending force test andapparatus noted above.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be achieved within the spirit and scopeof the invention.

1. A laminated light-blocking decorative article comprising: adecorative fabric having a face side and a back side, a dry foamedlayer, and a non-woven fabric having a face side and a back side,wherein the decorative fabric is laminated on its back side to the dryfoamed opacifying layer that is disposed on the back side of thenon-woven fabric, the dry foamed opacifying layer present at a drycoverage of less than or equal to 1000 g/m², and comprising: (a) porousparticles in an amount of at least 0.1 weight % and up to and including35 weight %, each porous particle comprising a continuous polymericphase and discrete pores dispersed within the continuous polymericphase, the porous particles having a mode particle size of at least 2 μmand up to and including 50 μm and a porosity of at least 20 volume % andup to and including 70 volume %; (b) a matrix material that is derivedfrom a (b) binder material, which matrix material is present in anamount of at least 10 weight % and up to and including 80 weight %, (c)two or more additives in an amount of at least 0.0001 weight % and up toand including 50 weight %, the two or more additives comprising at leastone foaming surfactant and at least one foam stabilizer, (d) an aqueousmedium in an amount of less than 5 weight %, and (e) an opacifyingcolorant in an amount of at least 0.002 weight % and up to and including2 weight %, which opacifying colorant being a different material fromthe (a) porous particles, (b) binder material, and (c) two or moreadditives, and which opacifying colorant absorbs electromagneticradiation having a wavelength of at least 380 nm and up to and including800 nm, all amounts of (a) porous particles, (b) binder material, (c)two or more additives, and (e) opacifying colorant being based on thetotal weight of the dry foamed opacifying composition.
 2. The laminatedlight-blocking decorative article of claim 1, wherein the non-wovenfabric is a blended or nonblended fabric.
 3. The laminatedlight-blocking decorative article of claim 1, wherein the non-wovenfabric is a spunlace non-woven fabric.
 4. The laminated light-blockingdecorative article of claim 1, wherein the non-woven fabric has a basisweight of at least 0.5 oz/yd² (16.95 g/m²) and up to and including 25oz/yd² (847.7 g/m²).
 5. The laminated light-blocking decorative articleof claim 1, wherein the non-woven fabric is colored.
 6. The laminatedlight-blocking decorative article of claim 1, wherein the decorativefabric is a woven fabric that is patterned, embossed, or printed.
 7. Thelaminated light-blocking decorative article of claim 1, wherein thedecorative fabric is a woven fabric having a repeating design patternthat is woven or embroidered into the decorative fabric.
 8. Thelaminated light-blocking decorative article of claim 1, wherein thedecorative fabric is a double cloth jacquard.
 9. The laminatedlight-blocking decorative article of claim 1, wherein either thenon-woven fabric or the decorative fabric, or both the non-woven fabricand the decorative fabric, comprise an antimicrobial agent, a fireretardant, or a soil release agent, or any combination thereof.
 10. Thelaminated light-blocking decorative article of claim 1, wherein thelaminated decorative article is a window shade.
 11. The laminatedlight-blocking decorative article of claim 1, wherein the (e) opacifyingcolorant is a carbon black, a neutral or black pigment or dye other thana carbon black, or a combination of two or more of such materials. 12.The laminated light-blocking decorative article of claim 1, wherein the(c) two or more additives further comprise one or more of anantimicrobial agent, a fire retardant, or both an antimicrobial agentand a fire retardant.
 13. The laminated light-blocking decorativearticle of claim 1, wherein the (b) binder material has a glasstransition temperature (T_(g)) of less than 25° C.
 14. The laminatedlight-blocking decorative article of claim 1, wherein the continuouspolymeric phase of the (a) porous particles comprises one or morecellulose polymers, a polyester, a polystyrene, or a combinationthereof.
 15. The laminated light-blocking article of claim 1, whereinthe (b) binder material comprises a crosslinkable material and a curingagent.
 16. The laminated light-blocking article of claim 1, wherein theat least one foaming surfactant and the at least one foam stabilizer areindependently one of the following compounds, or a mixture thereof:ammonium stearate, ammonium palmitate, sodium lauryl sulfate, ammoniumlauryl sulfate, ammonium or sodium alkyl sulfosuccinate, disodiumstearyl sulfosuccinate, diammonium n-octadecyl sulfosuccinamate,ethoxylated alcohols, a fatty acid soap, and a fatty acid condensationproduct with an alkylene oxide.
 17. The laminated light-blockingdecorative article of claim 1, wherein the (e) opacifying colorant ispresent in the aqueous foamed opacifying composition in an amount of atleast 0.001 weight % and up to and including 0.5 weight %, based on thetotal weight of the aqueous foamed opacifying composition.
 18. Thelaminated light-blocking decorative article of claim 1, wherein the (e)opacifying colorant is present solely within the (a) porous particles.19. The laminated light-blocking decorative article of claim 1, whereinthe aqueous foamed opacifying composition further comprises an adhesivematerial.